Relaxation Lifetime Research Articles

Photoelectric properties of the semiconductor Bi2YbO4Cl with broad spectral response

Bi2YbO4Cl with a fluorite layer structure belongs to the family of the bismuth rare-earth oxyhalides Bi2REO4X (X=Cl, Br, I). However, the synthesis and photoelectric properties of Bi2YbO4Cl have almost not been reported. In this work, Bi2YbO4Cl was synthesized using the solid-state method and the solvothermal method. Yb3+ ions show a strong characteristic absorption peak at 980 nm, which was measured by ultraviolet–visible–near-infrared absorption spectra. The transient photoconductivity of Bi2YbO4Cl was obtained by time-resolved terahertz spectroscopy system under 400 and 800 nm laser excitations, respectively. The frequency-dependent transient photoconductivity analysis reveals the Drude-Smith behavior in Bi2YbO4Cl. Under photoexcitation, the hot charge carriers with a long relaxation lifetime and a carrier mobility of 48 cm2/(V·s) are obtained. The synthesis of Bi2YbO4Cl is of great significance for the development of novel photocatalytic and photoharvesting materials with broad spectral response.

Magnetic-field coils for metastability-exchange optical pumping, spectroscopy, and magnetic resonance of helium.

Optical pumping on the 23S-23P transition (1083nm) of metastable 3He or 4He atoms is used for science and applications. Gas is usually enclosed in elongated cells with lengths ranging from several centimeters to several meters for efficient absorption. Good magnetic-field homogeneity is needed for weak diffusion-induced relaxation and long nuclear magnetic resonance (NMR) signal lifetimes. A compact coil system is designed using a target-oriented numerical optimization method. It provides a suitably uniform field over cell volumes, with characteristics depending on the chosen optimization parameters. Additional pairs of coils can be used to generate transverse field components with contributions to the total field inhomogeneities that are discussed.

Photoelectrochemical Water Splitting: A Visible-Light-Driven CoTiO3@g-C3N4-Based Photoanode Interface Follows the Type II Heterojunction Scheme.

Harnessing solar energy can be efficiently used to generate hydrogen by photochemical water splitting, which is a sustainable and environmentally benign energy source. Here, a unique visible-light-driven CoTiO3@g-C3N4 (CTOCN)-based photoanode interface has been optimized and developed with modification to follow the type II heterojunction for the enhancement of photoelectrochemical water splitting. Initially, a graphitic carbon nitride-loaded CoTiO3 (with 10 wt % g-C3N4) composite was obtained using a one-pot solvothermal method. Accordingly, the type II heterojunction interface between g-C3N4 and CoTiO3 has been successfully created and confirmed by the acquired phase, morphological, and optical examinations. Thereby, heterostructure generations with interfacial interaction were enabled to decrease photogenerated electron-hole pair recombination, leading to enhanced charge transfer for water oxidation kinetics. The minimal charge transfer resistance and hole relaxation lifetime (p) shown in Nyquist and Bode plots have further confirmed the rapid electron transport across the electrode/electrolyte interfaces, which is attributed to an enhanced absorption of holes for the water splitting process. Additionally, UV-vis spectroscopy, Mott-Schottky analysis, and UPS studies were used to determine the band edge locations of g-C3N4 and CoTiO3. In comparison to previously developed nanohybrids and their equivalents, the CTOCN-d photoanode follows the type II charge transfer mechanism, resulting in a higher photocurrent density of 55.51 mA cm-2.

Modulating Carrier Dynamics in PdSe2: The Role of Pressure in Electronic and Phononic Interactions.

PdSe2 is a puckered transition metal dichalcogenide that has been reported to undergo a two-dimensional to three-dimensional structural transition under pressure. Here, we investigated the electronic and phononic evolution of PdSe2 under high pressure using pump-probe spectroscopy. We observed the electronic intraband and interband transitions occurring in the d orbitals of Pd, revealing the disappearance of the Jahn-Teller effect under high pressure. Furthermore, we found that the decay rates of interband recombination and intraband relaxation lifetimes change at 3 and 7 GPa, respectively. First-principles calculations suggest that the bandgap closure slows the decay rate of interband recombination after 3 GPa, while the saturation of phonon-phonon scattering is the main reason for the relatively constant intraband relaxation lifetime. Our work provides a novel perspective for understanding the evolution of the electron and modulation of the carrier dynamics by phonons under pressure.

Manipulation and Mechanistic Understanding of Exciton Spin Dynamics in a Chiral Inorganic Nanosystem via Facile pH‐Regulation

AbstractThis study demonstrates effective manipulation of exciton spin dynamics in a prototypical chiral inorganic nanosystem, i.e., cadmium selenide (CdSe) nanosheets capped with chiral cysteine ligands in aqueous solution, via facile pH‐regulation that can directly modify the electronic coupling between CdSe and cysteine's thiol group through Cd─S bonding. The comparative scrutiny by using transient circular dichroism spectroscopy enables to decipher the pertinent mechanisms behind the pH‐regulated spin‐flip dynamics. The hole‐trapping interaction between the valence‐band heavy‐hole spin state of CdSe and the cysteine‐induced “extrinsic” surface state is found to play a dominant role in prolonging the hole spin relaxation lifetime (by more than threefold). This study also demonstrates a relevant application in modulating the sensitivity of circularly polarized light detection. This work sets a paradigm for harnessing the elusive interactions in chiral inorganic nanosystems to achieve desired spin‐polarization regulation, refreshing the fundamental understanding about the mechanisms of spin dynamics involved therein.

Evidence of abnormal hot carrier thermalization at van Hove singularity of twisted bilayer graphene

Interlayer twist evokes revolutionary changes to the optical and electronic properties of twisted bilayer graphene (TBG) for electronics, photonics and optoelectronics. Although the ground state responses in TBG have been vastly and clearly studied, the dynamic process of its photoexcited carrier states mainly remains elusive. Here, we unveil the photoexcited hot carrier dynamics in TBG by time-resolved ultrafast photoluminescence (PL) autocorrelation spectroscopy. We demonstrate the unconventional ultrafast PL emission between the van Hove singularities (VHSs) with a ∼4 times prolonged relaxation lifetime. This intriguing photoexcited carrier behavior is ascribed to the abnormal hot carrier thermalization brought by bottleneck effects at VHSs and interlayer charge distribution process. Our study on hot carrier dynamics in TBG offers new insights into the excited states and correlated physics of graphene twistronics systems.

Vanadium in silicon carbide: telecom-ready spin centres with long relaxation lifetimes and hyperfine-resolved optical transitions

Vanadium in silicon carbide (SiC) is emerging as an important candidate system for quantum technology due to its optical transitions in the telecom wavelength range. However, several key characteristics of this defect family including their spin relaxation lifetime (T1), charge state dynamics, and level structure are not fully understood. In this work, we determine the T1 of an ensemble of vanadium defects, demonstrating that it can be greatly enhanced at low temperature. We observe a large spin contrast exceeding 90% and long spin-relaxation times of up to 25 s at 100 mK, and of order 1 s at 1.3 K. These measurements are complemented by a characterization of the ensemble charge state dynamics. The stable electron spin furthermore enables high-resolution characterization of the systems’ hyperfine level structure via two-photon magneto-spectroscopy. The acquired insights point towards high-performance spin-photon interfaces based on vanadium in SiC.

Relaxation Editing in NMR Using a New Two-Dimensional Long-Lived Coherence Method for Mixture Analysis.

The exploration of metabolomics and targeted segments of proteins stands as a pivotal facet of Nuclear Magnetic Resonance (NMR) analysis, furnishing valuable insights into molecular architectures and potential therapeutic applications. The issue of spectral congestion frequently presents challenges in ascribing distinct peaks within the confines of both one-dimensional (1D) and two-dimensional (2D) NMR spectra. Numerous strategies have been proposed to resolve specific resonances in NMR spectra differentially. Among these approaches, relaxation editing emerges as a viable solution. In the realm of relaxation phenomena within NMR, Long-Lived States (LLS) and Long-Lived Coherences (LLC) manifest as promising phenomena, offering enhanced relaxation lifetimes in comparison to the traditional longitudinal (T1) and transverse (T2) relaxation times for coupled nuclear spins. Notably, LLC presents a pathway to attenuate uncoupled high-intensity peaks, effectively diminishing their impact. The foundation of this technique rests upon the premise that the relaxation lifetime in the rotating frame (T1ρ) remains smaller than TLLC. In pursuit of refining spectral assignments within complex mixtures, we introduce a new pulse sequence tailored for LLC Total Correlation Spectroscopy (LLC-TOCSY). This demonstrates efficacy in extracting LLC signals within configurations involving multiple coupled spins, thereby decluttering the spectrum and enhancing the accuracy of peak assignments. To validate the effectiveness of this method, a collection of samples was subjected to scrutiny, yielding compelling results.

Collective long-lived zero-quantum coherences in aliphatic chains.

In nuclear magnetic resonance, long-lived coherences constitute a class of zero-quantum (ZQ) coherences that have lifetimes that can be longer than the relaxation lifetimes T2 of transverse magnetization. So far, such coherences have been observed in systems with two coupled spins with spin quantum numbers I = 1/2, where a term S0T0+T0S0 in the density operator corresponds to a coherent superposition between the singlet S0 and the central triplet T0 state. Here, we report on the excitation and detection of collective long-lived coherences in AA'MM'XX' spin systems in molecules containing a chain of at least three methylene (-CH2-) groups. Several variants of excitation by polychromatic spin-lock induced crossing (poly-SLIC) are introduced that can excite a non-uniform distribution of the amplitudes of terms such as S0S0T0S0S0T0, S0T0S0S0T0S0, and T0S0S0T0S0S0. Once the radio frequency fields are switched off, these are not eigenstates, leading to ZQ precession involving all six protons, a process that can be understood as a propagation of spin order along the chain of CH2 groups before the reconversion into observable magnetization by a second poly-SLIC pulse that can be applied to any one or several of the CH2 groups. In the resulting 2D spectra, the ω2 domain shows SQ spectra with the chemical shifts of the CH2 groups irradiated during the reconversion, while the ω1 dimension shows ZQ signals in absorption mode with linewidths on the order of 0.1Hz that are not affected by the inhomogeneity of the static magnetic field but can be broadened by chemical exchange as occurs in drug screening. The ZQ frequencies are primarily determined by differences ΔJ between vicinal J-couplings.

Temporal Resolution of Activity-Related Solvation Dynamics in the TIM Barrel Enzyme Murine Adenosine Deaminase.

Murine adenosine deaminase (mADA) is a prototypic system for studying the thermal activation of active site chemistry within the TIM barrel family of enzyme reactions. Previous temperature-dependent hydrogen deuterium exchange studies under various conditions have identified interconnected thermal networks for heat transfer from opposing protein-solvent interfaces to active site residues in mADA. One of these interfaces contains a solvent exposed helix-loop-helix moiety that presents the hydrophobic face of its long α-helix to the backside of bound substrate. Herein we pursue the time and temperature dependence of solvation dynamics at the surface of mADA, for comparison to established kinetic parameters that represent active site chemistry. We first created a modified protein devoid of native tryptophans with close to native kinetic behavior. Single site-specific tryptophan mutants were back inserted into each of the four positions where native tryptophans reside. Measurements of nanosecond fluorescence relaxation lifetimes and Stokes shift decays, that reflect time dependent environmental reoroganization around the photo-excited state of Trp*, display minimal temperature dependences. These regions serve as controls for the behavior of a new single tryptophan inserted into a solvent exposed region near the helix-loop-helix moiety located behind the bound substrate, Lys54Trp. This installed Trp displays a significantly elevated value for ; further, when Phe61 within the long helix positioned behind bound substrate is replaced by a series of aliphatic hydrophobic side chains, the trends in mirror the earlier reported impact of the same series of function-altering hydrophobic side chains on the activation energy of catalysis, .The reported experimental findings implicate a solvent initiated and rapid (>ns) protein restructuring that contributes to the enthalpic activation barrier to catalysis in mADA.

Motional Narrowing Effects in the Excited State Spin Populations of Mn-Doped Hybrid Perovskites.

Spin-orbit coupling in the electronic states of solution-processed hybrid metal halide perovskites forms complex spin-textures in the band structures and allows for optical manipulation of the excited state spin-polarizations. Here, we report that motional narrowing acts on the photoexcited spin-polarization in CH3NH3PbBr3 thin films, which are doped at percentage-level with Mn2+ ions. Using ultrafast circularly polarized broadband transient absorption spectroscopy at cryogenic temperatures, we investigate the spin population dynamics in these doped hybrid perovskites and find that spin relaxation lifetimes are increased by a factor of 3 compared to those of undoped materials. Using quantitative analysis of the photoexcitation cooling processes, we reveal increased carrier scattering rates in the doped perovskites as the fundamental mechanism driving spin-polarization-maintaining motional narrowing. Our work reports transition-metal doping as a concept to extend spin lifetimes of hybrid perovskites.

Reconciling TD-DFT and CASPT2 electronic structure methods for describing the photophysics of DNA.

Time-dependent density functional theory (TD-DFT) and multiconfigurational second-order perturbation theory (CASPT2) are two of the most widely used methods to investigate photoinduced dynamics in DNA-based systems. These methods sometimes give diverse dynamics in physiological environments usually modeled by quantum mechanics/molecular mechanics (QM/MM) protocol. In this work, we demonstrate for the uridine test case that the underlying topology of the potential energy surfaces of electronic states involved in photoinduced relaxation is similar in both electronic structure methods. This is verified by analyzing surface-hopping dynamics performed at the QM/MM level on aqueous solvated uridine at TD-DFT and CASPT2 levels. By constraining the dynamics to remain on state we observe similar fluctuations in energy and relaxation lifetimes in surface-hopping dynamics in both TD-DFT and experimentally validated CASPT2 methods. This finding calls for a systematic comparison of the ES potential energy surfaces of DNA and RNA nucleosides at the single- and multi-reference levels of theory. The anomalous long excited state lifetime at the TD-DFT level is explained by trapping due to the tendency of TD-DFT in QM/MM schemes with electrostatic embedding to underestimate the energy of the state leading to a wrong energetic order. A study of the FC energetics suggests that improving the description of the surrounding environment through polarizable embedding or by the expansion of QM layer with hydrogen-bonded waters helps restore the correct state order at TD-DFT level. Thus by combining TDDFT with an accurate modeling of the environment, TD-DFT is positioned as the standout protocol to model photoinduced dynamics in DNA-based aggregates and multimers.

Bi2WO6 Incorporation of g‐C3N4 to Enhance the Photocatalytic N2 Reduction Reaction and Antibiotic Pollutants Removal

Synthesis of ammonia from photocatalytic N2 reduction is challenging due to the fast recombination of electron–hole pairs and the low selectivity of N2 on catalysts. This can be addressed by creating heterojunctions to separate the photogenerated carriers adequately. In this regard, BW/g‐C3N4 is synthesized and the weight percentage of g‐C3N4 is varied. The best photocatalytic activity for N2 reduction reaction (N2RR) is achieved with a ratio of BW/gC3N4 in 3.5:2 ratio, deemed to be the optimized heterojunction. N2‐temperature programmed desorption analysis shows outstanding chemisorption of N2 adsorbed on the BW/g‐C3N4 surface compared to pristine g‐C3N4 and BW. Additionally, forming a heterojunction enhances the charge transfer process and well‐separated electron–hole pairs, significantly boosting the water oxidation process on the catalytic surface. Photoelectrochemical analysis reveals that BW/g‐C3N4 exhibits the shortest hole relaxation lifetime and higher current density than its pristine counterparts. The robust contact between g‐C3N4 and BW reduces the work function of BW/g‐C3N4 based on ultraviolet photoelectron spectroscopy data. Ammonia production with the optimized BW/gC3N4‐3.5:2 is 5.3 and 2.1 times higher than pure g‐C3N4 and Bi2WO6, respectively. Meanwhile, BW/g‐C3N4 demonstrates excellent photocatalytic activity toward antibiotic pollutant degradation as well. After 150 min of visible light irradiation, the removal of 94% ciprofloxacin (CIP) is observed. Finally, a possible mechanism is proposed for photocatalytic N2RR and CIP degradation.

Layer engineering in optoelectronic and photonic properties of single and few layer phosphorene using first-principles calculations.

Developing devices for optoelectronic and photonic applications-based nanomaterials has been one of the most critical challenges in the last decade. In this work, we use first-principles density functional theory combined with non-equilibrium Green's function to highlight for the first time the sensitivity of optoelectronic and photonic properties toward the exfoliation process. All the studied structures were relaxed and their relevant phonon modes confirm the high structural stability. The obtained phosphorene layers remained semiconducting with a direct band gap like the respective bulk structure with 10 layers. We also examined the effects of the thickness on the electron-hole interaction by calculating absorption energy combined with electron relaxation lifetimes. Additionally, we explore the optoelectronic properties, which can also be influenced by the exfoliation. Finally, we found that the current-voltage (I-V) characteristic shows higher sensitivity toward the bulk structure than the other 2D forms of phosphorene structures, meaning that the Schottky barrier at the interface of the bulk phosphorene is much lower than mono, and few layer phosphorene.

Electrically tunable non-radiative lifetime in WS2/WSe2 heterostructures.

Van der Waals heterostructures based on transition metal dichalcogenides (TMDs) have emerged as excellent candidates for next-generation optoelectronics and valleytronics, due to their fascinating physical properties. The understanding and active control of the relaxation dynamics of heterostructures play a crucial role in device design and optimization. Here, we investigate the back-gate modulation of exciton dynamics in a WS2/WSe2 heterostructure by combining time-resolved photoluminescence (TRPL) and transient absorption spectroscopy (TAS) at cryogenic temperatures. We find that the non-radiative relaxation lifetimes of photocarriers in heterostructures can be electrically controlled for samples with different twist-angles, whereas such lifetime tuning is not present in standalone monolayers. We attribute such an observation to doping-controlled competition between interlayer and intralayer recombination pathways in high-quality WS2/WSe2 samples. The simultaneous measurement of TRPL and TAS lifetimes within the same sample provides additional insight into the influence of coexisting excitons and background carriers on the photo-response, and points to the potential of tailoring light-matter interactions in TMD heterostructures.

Terahertz Metamaterial Sensor Based on Electromagnetic Induced Transparency

A graphene-based terahertz electromagnetically induced transparency (EIT) metamaterial sensor is proposed and studied. The sensor is made up of two bright modes: a graphene strip resonator and a 7-shape resonator. In a terahertz metamaterial sensor based on EIT, the metamaterial structure is designed to have two resonant modes that are coupled through a common resonator. When terahertz radiation hits the metamaterial, the two resonant modes interact, creating a window of transparency in the transmission spectrum. It illuminated that the physical mechanism of the EIT effect lay in the recombination effect of the conductive resonators. By changing the carrier relaxation lifetime or the Fermi energy of the graphene, the amplitude or the location of the EIT window could be actively tuned. The terahertz metamaterial sensors based on EIT have the potential to provide highly accurate and sensitive measurements in a wide range of fields and could lead to important advances in medical diagnostics.

Gram-scale synthesis of highly doped chlorine graphene quantum dots: Synthesis and photoluminescence properties

Band-gap engineering of graphene-based nanomaterials has a huge influence on their optical and structural properties. Our contribution reports the successful gram-scale synthesis of highly chlorinated graphene quantum dots (Cl-GQDs) via a two-step preparation method. X-ray photoelectron spectroscopy (XPS) proved the successful doping of chlorine atoms into the as-prepared graphene oxide quantum dots (O-GQDs). Time-resolved fluorescence revealed a high decrease in the relaxation lifetime from 690 ps for O-GQDs to 5.3–4 ps for Cl-GQDs. Transmission electron microscopy (TEM) confirms that all nanoparticles are on the quantum scale (4–6 nm). The large blueshift in photoluminescence (PL) 150 nm from the original O-GQD (440 → 290 nm) supports the chlorination effect which enables tuning the band gap of O-GQD.

BaCuZnSeS material as advanced chalcogenide semiconductor: Synthesis, 3D morphology and electrochemistry

Advanced BaCuZnSeS (BCZSeS) material with a 3D stalagmite structure on a flower-like surface is successfully prepared by hydrothermal process. The structural, morphological and thermal properties of BCZSeS are analyzed. Electrodes were prepared by the doctor blade method and annealed at 500 °C for different time periods. A minimum charge transfer resistance (Rct) of 7.7 ohm.cm2, high diffusion coefficient of 2.73 × 10-3 cm2/s and maximum electron relaxation lifetime of 0.3 ms have been achieved for optimized BCZSeS based electrode.

Alignment-Based Optically Pumped Magnetometer Using a Buffer-Gas Cell

Alignment-based optically pumped magnetometers (OPMs) are capable of measuring oscillating magnetic fields with high sensitivity in the $\mathrm{fT}/\sqrt{\mathrm{Hz}}$ range. Until now, alignment-based magnetometers have only used paraffin-coated vapour cells to extend the spin relaxation lifetimes of the alkali vapour. The drawback of these cells is that they are hand blown and are therefore time intensive, and somewhat unreliable, to produce. Buffer-gas cells, on the other hand, can be manufactured on a mass scale using microfabrication techniques. In this work we use hand-blown cells, but our methods also apply to microfabricated buffer-gas cells. We present the first demonstration of an alignment-based magnetometer using a buffer-gas vapour cell containing caesium (Cs) alkali vapour and nitrogen (${\mathrm{N}}_{2}$) buffer gas. The OPM is operated at $55{\phantom{\rule{0.1em}{0ex}}}^{\ensuremath{\circ}}\mathrm{C}$ and we achieve a $325\phantom{\rule{0.2em}{0ex}}\mathrm{fT}/\sqrt{\mathrm{Hz}}$ sensitivity to 10 kHz oscillating magnetic fields with an 800 Hz bandwidth. The alignment-based magnetometer uses a single low-power laser beam for optical pumping and probing and could potentially allow for more rapid commercialization of radio-frequency OPMs, due to the robustness of the one-beam geometry.

Strongly anisotropic ultrafast dynamic behavior of GaTe dominated by the tilted and flat bands

The anisotropic transport properties of gallium telluride (GaTe) have been reported by several experiments, giving rise to many debates recently. The anisotropic electronic band structure of GaTe shows the extreme difference between the flat band and tilted band in two distinct directions, - and - , and which we called as the mixed flat-tilted band (MFTB). Focusing on such two directions, the relaxation of photo-generated carriers has been studied using the non-adiabatic molecular dynamics (NAMD) method to investigate the anisotropic behavior of ultrafast dynamics. The results show that the relaxation lifetime is different in flat band direction and tilted band direction, which is evidence for the existence of anisotropic behavior of the ultrafast dynamic, and such anisotropic behavior comes from the different intensities of electron–phonon coupling of the flat band and tilted band. Furthermore, the ultrafast dynamic behavior is found to be affected strongly by spin–orbit coupling (SOC) and such anisotropic behavior of the ultrafast dynamic can be reversed by SOC. The tunable anisotropic ultrafast dynamic behavior of GaTe is expected to be detected in ultrafast spectroscopy experiments and it may provide a tunable application in nanodevice design. The results may also provide a reference for the investigation of MFTB semiconductors.